CN110940756B - Method for evaluating quality of rhizoma acori graminei - Google Patents
Method for evaluating quality of rhizoma acori graminei Download PDFInfo
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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Abstract
The invention relates to the technical field of traditional Chinese medicine detection, and particularly discloses a method for evaluating the quality of rhizoma acori graminei, which specifically comprises the following steps: step 1, preparing a standard solution; step 2, preparing a test solution; step 3, determination; and 4, analyzing. The method for evaluating the quality of the acorus gramineus can detect 61 volatile components in the acorus gramineus, can evaluate the quality of the acorus gramineus medicinal material according to the content information of the 61 volatile components, and can be used for distinguishing the quality of the acorus gramineus in different producing areas; according to the detection method, the difference of the types and the contents of the compounds in the extraction process of the rhizoma acori graminei can be analyzed, so that the emulsification phenomenon in the extraction process of the rhizoma acori graminei volatile oil is controlled, a reference is provided for the efficient extraction of the Chinese medicinal material volatile oil, and the yield and the quality of the industrial large-scale production of the volatile oil are effectively improved.
Description
Technical Field
The invention relates to the technical field of traditional Chinese medicine detection, and particularly discloses a method for evaluating the quality of rhizoma acori graminei.
Background
Rhizoma acori graminei has the effects of inducing resuscitation and eliminating phlegm, inducing resuscitation and benefiting intelligence, and resolving dampness and stimulating appetite, volatile oil is a main effective substance of the rhizoma acori graminei, and the main components of the rhizoma acori graminei comprise beta-asarone, gamma-asarone, beta-caryophyllene and the like. The quality control of the grass-leaved sweetflag plays an important role in the safe use and quality of the grass-leaved sweetflag.
In the prior art, the quality control method of acorus gramineus soland usually takes the total amount of volatile oil as a control index, and the total amount is determined according to a volatile oil determination method (appendix X D) specified in Chinese pharmacopoeia. The product contains volatile oil of not less than 1.0% (ml/g), or the single component of beta-asarone and alpha-asarone in the volatile oil of rhizoma Acori Graminei is used as the index component for quality control, but the two control methods are not beneficial to the comparison and differentiation of the quality of rhizoma Acori Graminei in different producing areas.
Disclosure of Invention
In order to solve the above problems, the invention provides a method for evaluating the quality of acorus gramineus, which specifically comprises the following steps:
accurately weighing a tetradecanol standard substance, adding absolute ethyl alcohol for dissolving, and fixing the volume to obtain a tetradecanol standard substance solution; accurately weighing a docosane standard substance, adding absolute ethyl alcohol to dissolve, and fixing the volume to obtain a docosane standard substance solution;
a. weighing rhizoma Acori Graminei, extracting by steam distillation, standing the extractive solution for layering, and separating oil phase and water phase;
b. adding absolute ethyl alcohol into the oil phase obtained by separation in the step a, diluting the solution with constant volume to 10mL, adding distilled water into the solution with constant volume to dilute by 100 times, and adding the tetradecanol standard solution and the docosane standard solution in the step 1 respectively to serve as volatile oil sample solutions;
c. taking the aqueous phase solution obtained by separation in the step a, and respectively adding the tetradecanol standard solution and the docosane standard solution prepared in the step 1 as aromatic water test sample solutions;
precisely absorbing the volatile oil test solution and the aromatic water test solution obtained in the step 2, and injecting the volatile oil test solution and the aromatic water test solution into a gas chromatography-mass spectrometer for determination, wherein the chromatographic conditions are as follows:
a chromatographic column: HP-5 MS quartz capillary column; the temperature programming method comprises maintaining at 50 deg.C for 2 min and 5 deg.C/min-1Increasing the speed to 110 ℃, keeping the speed for 2 min, and then increasing the speed to 2 ℃ for min-1The rate is increased to 120 ℃ and maintained for 5 min, then 4 ℃ min-1Raising the speed to 200 ℃, and keeping for 2 min; finally at 10 ℃ min-1The speed is increased to 280 ℃ and kept for 10 min;
mass spectrum conditions: selecting an EI ion source, wherein the scanning mass range is 30-500 amu, and the solvent delay time is 3 min;
step 4, analysis:
calculating and analyzing the relative content of the characteristic components in the volatile oil test solution and the aromatic water test solution and the total amount of the volatile oil by using a PCA method, and distinguishing the quality and the producing area of the rhizoma acori graminei medicinal material according to the analysis result;
wherein the characteristic components are isoeugenol methyl ether, 2,4, 5-trimethoxy-1-propenyl benzene, cyperenone, methyl eugenol and cis-methyl isoeugenol.
Preferably, the mass concentration of the tetradecanol standard solution in the step 1 is 2.06 mg/mL-1The mass concentration of the docosane standard solution is 2.06 mg-mL-1。
Preferably, the extraction method of Acorus tatarinowii Schott in the step a comprises the following steps: weighing rhizoma Acori Graminei, pulverizing, sieving with a first sieve, adding water 10 times of the total weight of rhizoma Acori Graminei, extracting for 6 hr by steam distillation, collecting extractive solution every 30 min, recording the volume of the collected solution, adding distilled water of equal volume into the extraction container, standing the extractive solution until oil and water are separated, and separating oil phase and water phase.
Preferably, the volume ratio of the diluted constant volume solution to the tetradecanol standard solution and the docosane standard solution in the step b is 100: 1.
Preferably, the volume ratio of the aqueous phase solution to the tetradecanol standard solution and the docosane standard solution in step c is 1: 100.
Preferably, the carrier gas in the step 3 is helium, the split ratio is 10:1, and the injection port temperature is 230 ℃; the ion source temperature is 230 ℃, the interface temperature is 250 ℃, and the quadrupole rod temperature is 150 ℃.
Preferably, the relative amounts of the volatile components are calculated using an internal standard method.
The invention also provides a method for controlling the emulsification phenomenon in the extraction process of the rhizoma acori graminei volatile oil, which comprises the following specific control methods: weighing rhizoma Acori Graminei, adding 10 times of water, and extracting by steam distillation for 3-3.5 hr.
Compared with the prior art, the invention has the beneficial effects that:
the method for evaluating the quality of the acorus gramineus can detect 61 volatile components (11 oil-water coexisting components in the acorus gramineus) in the acorus gramineus, calculate and analyze the volatile component content information in the 61 by using a PCA method, and evaluate the quality of the acorus gramineus medicinal material according to the analysis result, and the detection method takes a plurality of components as quality control indexes, so that the result is more reliable, and meanwhile, the method can be used for distinguishing the quality of the acorus gramineus in different producing areas or identifying the producing areas of the acorus gramineus; according to the detection method, the difference of the types and the contents of the compounds in the extraction process of the rhizoma acori graminei can be analyzed, so that the emulsification phenomenon in the extraction process of the rhizoma acori graminei volatile oil is controlled, a reference is provided for the efficient extraction of the Chinese medicinal material volatile oil, and the yield and the quality of the industrial large-scale production of the volatile oil are effectively improved.
Drawings
FIG. 1 is a total ion flow diagram of volatile components of Acorus tatarinowii Schott;
FIG. 2 is a feature map of the extracted components of Acorus tatarinowii Schott; wherein, A commands the extraction characteristic map of the hair oil component; b refers to the aromatic water component characteristic spectrum;
FIG. 3 is a time-content curve of the main characteristic compounds for different distribution cycles; wherein the dots represent different compounds; the line represents the time-content curve of the corresponding compound;
FIG. 4 is the correlation of compounds in water only with major characteristic components; wherein a refers to the correlation between the main characteristic component in water and the compound only in water; b refers to the correlation of the main characteristic components in the oil with the compounds in water only;
FIG. 5 is a radar signature for different physicochemical parameters of different components; wherein A represents a radar profile of different physicochemical parameters of an oil and water common compound; b represents the radar signatures of different physicochemical parameters of compounds only in oil, C represents the radar signatures of different physicochemical parameters of compounds only in water;
FIG. 6 is a main component analysis spectrum of the distribution of volatile components of Acorus gramineus soland;
FIG. 7 shows PCA analysis results of Acorus gramineus soland in different producing areas.
Detailed Description
In order to make the technical solutions of the present invention better understood and enable those skilled in the art to practice the present invention, the following embodiments are further described, but the present invention is not limited to the following embodiments.
The instruments and materials used in the examples were as follows:
BT-25S type one hundred thousand electronic balance, sandelis shanghai trading ltd; agilent7890B/5977B gas chromatography-mass spectrometer, Agilent, USA;
the docosane standard substance and the tetradecanol standard substance are purchased from Shanghai leaf biology Limited company (the batch numbers are A0388218 and A11N8L47966 respectively, and the contents are respectively more than or equal to 99 percent and more than or equal to 99 percent);
the rhizoma acori graminei medicinal material is purchased from Shanxi Xingsheng De pharmaceutical industry, Limited liability company, and is identified as the dried rhizome of Acorus tatarinowii Schott of Araceae plant by professor Yonggang in crude drug research laboratory of Shanxi Chinese medicine university;
absolute ethanol was analytically pure.
Examples
A method for evaluating the quality of rhizoma acori graminei specifically comprises the following steps:
accurately weighing 20.6mg to 10mL of tetradecanol standard substance in a volumetric flask, adding absolute ethyl alcohol to dissolve, and fixing the volume to a scale to obtain the mass concentration of 2.06 mg/mL-1A tetradecanol standard solution; precisely weighing 20.6 mg-10 mL of docosane standard substance in a volumetric flask, adding absolute ethyl alcohol to dissolve and fixing the volume to a scale to obtain the mass concentration of 2.06 mg-mL-1A docosane standard solution;
a. accurately weighing 201.35 g of rhizoma Acori Graminei, pulverizing, sieving with pharmacopeia I sieve, adding 10 times of water, extracting volatile oil by steam distillation for 6h (timing when the medicinal liquid is boiling), collecting extractive solution every 30 min, recording the volume of the collected solution, and adding equal volume of distilled water into the round-bottom flask; after the extracting solution is static until oil and water are layered, separating oil and water parts which are respectively numbered as oil _0.5 h-oil _6h and water _0.5 h-water _6h, and storing at 4 ℃ for later use;
b. b, dissolving the volatile oil part obtained by separation in the step a by using absolute ethyl alcohol, fixing the volume to a 10mL volumetric flask, precisely transferring 1 mL to 100 mL volumetric flasks, adding distilled water to fix the volume to a scale mark, precisely transferring 5 mL to 20 mL headspace sample bottles, respectively adding 50 mu L of tetradecanol standard solution and docosane standard solution, and sealing by a gland to obtain volatile oil sample solution;
c. taking 5-20 mL headspace sample bottles of the aromatic water solution separated in the step a, respectively adding 50 mu L of tetradecanol standard solution and docosane standard solution, and sealing by a gland to obtain an aromatic water test sample solution;
precisely absorbing 1 mu L of volatile oil test solution and aromatic water test solution, and injecting into a gas chromatography-mass spectrometer for measurement;
wherein, the chromatographic conditions are as follows:
gas phase conditions: an HP-5 MS quartz capillary column (30 m multiplied by 0.25 mm multiplied by 0.25 mu m) is adopted, helium (purity 99.999%) is taken as carrier gas, the split ratio is 10:1, the injection port temperature is 230 ℃, and the temperature programming is carried out: initial temperature of 50 deg.C, holding for 2 min at 5 deg.C/min-1The speed is increased to 110 ℃, kept for 2 min at 2 ℃ min-1The rate is increased to 120 ℃, kept for 5 min at 4 ℃ min-1The speed is increased to 200 ℃, kept for 2 min and finally 10 ℃ min-1The speed is increased to 280 ℃ and kept for 10 min;
mass spectrum conditions: the EI ion source has the ion source temperature of 230 ℃, the interface temperature of 250 ℃, the quadrupole rod temperature of 150 ℃, the scanning mass range of 30-500 amu and the solvent delay of 3 min.
The GC-MS spectrum of the volatile component of rhizoma Acori Graminei obtained by the above detection method is shown in FIG. 1, and FIG. 1 shows that under the chromatographic conditions, each component can be basically separated.
Analyzing the volatile component information of the grassleaf sweelflag rhizome by analyzing a GC-MS spectrogram of the volatile component of the grassleaf sweelflag rhizome:
1. analysis of Compounds
Calling NIST14.L compound spectrum library, analyzing the total ion flow diagram, sorting the compound information, and measuring 61 volatile components of rhizoma Acori Graminei at the time, as shown in Table 1.
TABLE 1 volatile component compound information of Acorus gramineus
| Numbering | CAS number | Name of Compound | Molecular weight/ |
| 1 | 000140-67-0 | Estragole (Estragole) | 148.089 |
| 2 | 000093-16-3 | Benzene,1,2-dimethoxy-4- (1-propenyl) - (isoeugenol methyl ether) | 178.099 |
| 3 | 158930-41-7 | Eremophila ketone (jasmine love) | 220.183 |
| 4 | 005273-86-9 | Beta. Asarone (beta-Asarone) | 208.11 |
| 5 | 1000313-34-5 | 1,2-Dimethoxy-4- (2-methoxy-1-propenyl) bezene (1, 2-Dimethoxy-4-2-methoxy-1-propane) Alkenyl-benzenes | 208.11 |
| 6 | 1000410-08-2 | 7-[2-(4-Methoxyphenyl)ethenyl]-2-methyl-3-phenylpyrazolo[1,5-a]pyrimidine 7- [2- (4-methoxyphenyl) ethenyl]-2-methyl-3-phenylPyrazolo [1,5-a]Pyrimidines | 341.153 |
| 7 | 003466-15-7 | (3aR,4R,7R)-1,4,9,9-Tetramethyl-3,4,5,6,7,8-hexahydro-2H-3a,7- Methanoazulen-2-one (cyperenone) | 218.167 |
| 8 | 000093-15-2 | Methyleugenol (methyl eugenol) | 178.099 |
| 9 | 015438-94-5 | (1S,5S,6R)-6-Methyl-2-methylene-6-(4-methylpent-3-en-1-yl)bicyclo[3.1.1] heptanane (hydrated camphene) | 204.188 |
| 10 | 006380-24-1 | Benzene,1, 2-dimethoxy-4-propenyl-, (Z) - (cis-methyl isoeugenol) | 178.099 |
| 11 | 006831-17-0 | 2H-Cyclopropa[a]naphthalen-2-one,1,1a,4,5,6,7,7a,7b-octahydro-1,1,7,7a- tetramethyl-, (1a.alpha.,7.alpha.,7a.alpha.,7b.alpha.) - (aristolocone) | 218.167 |
| 12 | 063673-76-7 | 2-Chloro-4- (4-methoxyphenyl) -6- (4-nitrophenyl) pyrimidine (2-Chloro-4- (4-methoxy-phenyl) Phenyl) -6- (4-nitrophenyl) pyrimidine) | 341.057 |
| 13 | 006754-66-1 | 5(1H)-Azulenone,2,4,6,7,8,8a-hexahydro-3,8-dimethyl-4-(1- methythienylidene) -, (8S-cis) - (citrine) | 218.167 |
| 14 | 000470-82-6 | Eucalyptol (Eucalyptol) | 154.136 |
| 15 | 016729-01-4 | 1-isoproyl-4, 7-dimethyl-1,2,3,5,6,8a-hexahydronaphthalene (4, 7-dimethyl-1- Propan-2-yl-1, 2,3,5,6,8 a-hexahydronaphthalene) | 204.188 |
| 16 | 000071-41-0 | 1-Pentanol (n-Pentanol) | 88.089 |
| 17 | 000066-25-1 | Hexanal (Hexanal) | 100.089 |
| 18 | 005794-04-7 | Bicyclo[2.2.1]heptane, 2, 2-dimethyl-3-methyl-, (1S) - (-) -camphene) | 136.125 |
| 19 | 000100-52-7 | Benzaldehyde (Benzaldehyde) | 106.042 |
| 20 | 003391-86-4 | 1-Octen-3-ol (1-vinyl hexanol) | 128.12 |
| 21 | 000589-98-0 | 3-Octanol (3-Octanol) | 130.136 |
| 22 | 000078-70-6 | Linalool (Linalool) | 154.136 |
| 23 | 000464-49-3 | (+) -2-Bornanone (camphene) | 152.12 |
| 24 | 000465-31-6 | Bicyclo[2.2.1]heptan-2-ol, 2,3,3-trimethy- (hydrated camphene) | 154.136 |
| 25 | 000464-45-9 | Bicyclo[2.2.1]heptan-2-ol, 1,7, 7-trimetyl-, (1S-endo) - (L-borneol) | 154.136 |
| 26 | 020126-76-5 | 3-Cyclohexen-1-ol, 4-methyl-1- (1-methythyyl) -, (R) - (-) -4-terpineol) | 154.136 |
| 27 | 024587-27-7 | 1,3,5-Hexatriene, 3-methyl-, (Z) - ((3Z) -3-methyl-1, 3, 5-Hexatriene) | 94.078 |
| 28 | 039020-72-9 | (2R,3R,6S) -6-isoproyl-3-methyl-2- (prop-1-en-2-yl) -3-vinylcyclohexane (Table) Acorus calamus ketone) | 220.183 |
| 29 | 005353-15-1 | Gamma. Asarone (gamma-Asarone) | 208.11 |
| 30 | 021698-46-4 | (3S,6S) -6-isoproyl-3-methyl-2- (propan-2-ylidine) -3-vinylcyclohexane (iso-naphthalene) Acorus calamus ketone) | 220.183 |
| 31 | 1000188-66-5 | 2(1H)Naphthalenone,3,5,6,7,8,8a-hexahydro-4,8a-dimethyl-6-(1- methyl thenyl) - (3,5, 6,7,8,8 a-hexahydro-4, 8 a-dimethyl-6- (1-methylvinyl) -2-naphthalenone) | 218.167 |
| 32 | 000562-74-3 | Terphin-4-ol (4-terpene alcohol) | 154.136 |
| 33 | 001888-90-0 | 3-Methylenecyclohexexene (3-methylene cyclohexene) | 94.078 |
| 34 | 351060-78-1 | Furane-3-carboxylic acid, 2-methyl-, [2-(4-fluorophenylamino)-2-oxo] ethyl ester (2-methyl-furan-3-carboxylic acid (4-fluorophenylcarbamoyl) methyl ester) | 277.075 |
| 35 | 007212-44-4 | 1,6,10-Dodecatrien-3-ol, 3,7, 11-trimetyl- (nerolidol) | 222.198 |
| 36 | 018908-20-8 | 2,5-Furandione, dihydro-3- (2-methyl-2-propenyl) - ((2-methyl-2-propene) succinic anhydride) | 154.063 |
| 37 | 001137-12-8 | 1,2,4-Methenoazulene,decahydro-1,5,5,8a-tetramethyl-,[1S-(1.alpha., 2.alpha.,3a.beta.,4.alpha.,8a.beta.,9R*)]- (+) -longifolene) | 204.188 |
| 38 | 000515-13-9 | Cyclohexane,1-ethenyl-1-methyl-2,4-bis(1-methylethenyl)-, [1S-(1.alpha., 2.beta.,4.beta.)]- ((-) -beta-elemene) | 204.188 |
| 39 | 017334-55-3 | 1H-Cyclopropa[a]naphthalene,1a,2,3,5,6,7,7a,7b-octahydro-1,1,7,7a- tetramethyl-,[1aR-(1a.alpha.,7.alpha,7a.alpha,7b.alpha.)]- (Calamus alkene) | 204.188 |
| 40 | 020307-83-9 | Cyclohexene,3-(1,5-dimethyl-4-hexenyl)-6-methylene-, [S-(R*,S*)]- （（-)β- Sesquiterpenoid) | 204.188 |
| 41 | 021747-46-6 | 1H-Cycloprop[e]azulene,1a,2,3,5,6,7,7a,7b-octahydro-1,1,4,7-tetramethyl-, [1aR-(1a.alpha.,7.alpha.,7a.beta.,7b.alpha.)]- (+) -Hornene) | 204.188 |
| 42 | 000489-40-7 | 1H-Cycloprop[e]azulene,1a,2,3,4,4a,5,6,7b-octahydro-1,1,4,7-tetramethyl-, [1aR-(1a.alpha.,4.alpha.,4a.beta.,7b.alpha.)]- (alpha-bronze alkene) | 204.188 |
| 43 | 000079-92-5 | Camphene (Camphor terpene) | 136.125 |
| 44 | 000464-48-2 | Bicyclo[2.2.1]heptan-2-one,1,7, 7-trimetyl-, (1S) - (1S) - (levo-camphor) | 152.12 |
| 45 | 005989-08-2 | Tricyclo[5.4.0.0(2,8)]undec-9-ene,2,6,6,9-tetramethyl-, (1R,2S,7R,8R)- (+) -alpha-longipinene)) | 204.188 |
| 46 | 110823-68-2 | Cyclohexane, 1-ethyl-1-methyl-2, 4-bis (1-methyl-beta-elemene) | 204.188 |
| 47 | 000087-44-5 | Caryophyllene (1-Caryophyllene) | 204.188 |
| 48 | 000088-84-6 | Beta. -guaifene (beta-guaialene) | 204.188 |
| 49 | 000495-61-4 | Beta. -Bisabolene (beta-Bisabolene) | 204.188 |
| 50 | 021698-44-2 | (2S,3S,6S) -6-isoproyl-3-methyl-2- (prop-1-en-2-yl) -3-vinylcyclohexane (water) Calamus ketone | 220.183 |
| 51 | 000067-51-6 | 3,5-Dimethylpyrazole (3, 5-Dimethylpyrazole) | 96.069 |
| 52 | 000473-08-5 | 7-Isopropenyl-1,4a-dimethyl-4,4a,5,6,7,8-hexahydro-3H-naphthalen-2-one(α- Cypernone) | 218.167 |
| 53 | 000098-01-1 | Furfural (Furfural) | 96.021 |
| 54 | 000507-70-0 | endo-Borneol (2-alcohol) | 154.136 |
| 55 | 017122-79-1 | Benzoic acid, 4- (2-hydroxyiminoacetamido) - ((E) -4- (2- (hydroxyimino) acetamido) Benzoic acid ethyl ester) | 236.08 |
| 56 | 000498-60-2 | 3-Furaldehyde (3-furfural) | 96.021 |
The common components of the volatile oil and the aromatic water are measured to be 11 such as beta-Asarone (beta-Asarone CAS: 005273-86-9), Methyleugenol (methyl eugenol, CAS: 000093-15-2), Benzene,1,2-dimethoxy-4- (1-propenyl) - (isoeugenol methyl ether, CAS: 000093-16-3), Eremophila ketone (jasmone, CAS: 158930-41-7), and the like.
2. Extraction characteristic analysis of volatile components of rhizoma acori graminei
Calculating the content of volatile components of rhizoma Acori Graminei at different extraction time, and further drawing a heat map of volatile extraction characteristics of rhizoma Acori Graminei, as shown in FIG. 2.
From fig. 2A, it can be seen that a large amount of volatile oil components were collected 3 hours before extraction, and from volatile component clustering, the main components can be classified into 3 types: 6 components such as beta-Asarone (beta-Asarone, CAS: 005273-86-9) and the like, 4 components such as Methyleugenol CAS: 000093-15-2) and the like, and 5 components such as 5(1H) -Azulenone,2,4,6,7,8,8a-hexahydro-3,8-dimethyl-4- (1-methyltetrahydroylene) -, (8S-cis) - (citrinone, CAS: 006754-66-1) and the like, wherein the content of the component I is more. As can be seen from FIG. 2B, the main components in the aromatic water are dissolved out in large quantities 4 h before extraction, and the main components can be classified into 5 categories according to the clustering of volatile components, wherein the contents of the components (i), (ii) and (iii) are higher.
3. Feature component extraction
Drawing a characteristic component extraction time-content relation map, and obtaining a result shown in figure 3.
As can be seen from fig. 3, 4 components of beta, Asarone, Methyleugenol, Benzene,1, 2-dimethyl-4- (1-propenyl) -, Eremophila ketone are compounds shared by the volatile oil portion/aromatic water portion, and the content distribution of the 4 components in the volatile oil and aromatic water is in a significant opposite relationship, i.e., when there is a large amount of distribution in the volatile oil, the distribution in water decreases, and when there is a large amount of distribution in water, the distribution in oil decreases. Benzene,1, 2-dimetxy-4-propynyl-, (Z), 7- [2- (4-Methoxyphenyl) ethyl ] -2-methyl-3-phenylpyrazolo [1,5-a ] pyrimidine is a uniquely distributed component in volatile oils that has some correlation, but is not significant, with the distribution of other components in the volatile oil; gamma-Asarone and caryophylelene are specific main components in aromatic water, and particularly, the extraction rule of gamma-Asarone has extremely high similarity with the distribution rule of the main components in aromatic water, so that the components are supposed to be specifically distributed in water, play the role of an emulsifier and further mediate a large amount of other components to be distributed in water, thereby increasing the emulsification phenomenon of the whole oil-water system and reducing the content of the main components in a volatile oil part.
4. Influence of specific components in water on characteristic component extraction behavior
The experiment further calculates the sum of the contents of the specific components in the water at different extraction time points, and the correlation between the specific components in the water and the extraction behavior of the main components is considered as a whole, and the result is shown in figure 4.
As can be seen from FIG. 4A, the content of 1, 2-methoxy-4-1-propenyl-bezene, beta. -Asarone, Methyleugenol, which is the main characteristic component in the fragrant water, is significantly increased with the increase of the content of the specific component in the fragrant water, and is significantly positively correlated. As shown in FIG. 4B, the variation of the specific components in water and the main components in the volatile oil, beta, Asarone, Eremophila ketone and Estragole all show negative correlation variation rules, which indicates that the specific components in water actually reduce the content of the main components in the volatile oil.
5. Analysis of factors affecting the distribution of components
The physical and chemical properties of the specific components in water, the specific components in oil and the common components of oil and water, including water solubility, boiling point, molecular weight, flash point, density, polarizability, surface tension and the like are respectively inquired, the average value of the physical and chemical parameters of different components is calculated, the numerical normalization processing is carried out on the different physical and chemical parameters, and the result is shown in figure 5.
As shown in FIG. 5, the oil-water-shared component has the highest vapor pressure and the lowest water solubility, and the remaining properties are at intermediate levels. The polar surface area and boiling point of the specific components in the oil are high, the vapor pressure is very low, and the remaining properties are at intermediate levels. The water solubility and boiling point of only the components in water are extremely high, the vapor pressure is the lowest, and the other factors are all in the middle.
6. Further exploring the main components of the influence of different physical and chemical properties of the compound on the distribution behavior of the components
Through analysis, 11 principal components are obtained in total, the cumulative variance contribution rate of the first two principal components reaches 61%, wherein, PC1=0.14681259 × water solution-0.37560975 × molecular mass-0.20605110 × density-0.43829224 × bonding point-0.09136644 × vacuum pressure-0.26798843 × engineering of variance-0.46616729 × flash point-0.22616967 × index of resolution-0.10783966 × polar surface area-0.39483960 × polar analysis-0.29436075 × surface tension, the variance contribution rate is 37.4%, and the variance contribution rate is a positive water-soluble related principal component. PC2= 0.39982324 × water solution-0.28518538 × molecular mass +0.47577332 × density-0.04497843 × bonding point-0.02873476 × vacuum pressure-0.01508251 × Enthalpy of vacuum +0.02093713 × flash point +0.23001094 × index of recovery + 0.50185779 × polar surface area-0.31714286 × polar ability +0.35155364 × surface tension, the variance contribution rate is 23.3%, and the results are shown in FIG. 6.
As can be seen from fig. 6, when the value of PC1 for the main distribution of components is-4 to 2, the components alone in water, the components alone in oil, and the oil-water common components are not completely separated, and it is assumed that these factors may be only partial factors of the difference in oil-water distribution. According to the radar characteristic spectrum, the water solubility, the boiling point, the vapor pressure, the polar surface area and the like are main factors influencing the distribution of the components in water or oil, namely, the components with high vapor pressure can be distributed in water and oil; the components with high water solubility and high boiling point are easier to distribute in water; while components with high polar surface areas are more easily distributed in the oil.
7. Identification of different producing areas of acorus gramineus
The experiment collects 3 batches of grassleaf sweelflag rhizome medicinal materials in different producing areas, the grassleaf sweelflag rhizome medicinal materials are respectively from northern areas, southern areas and southwest areas, and the total amount of volatile oil components in the grassleaf sweelflag rhizome in the different producing areas and the contents of isoeugenol methyl ether, 2,4, 5-trimethoxy-1-propenyl benzene, cyperenone, methyl eugenol and cis-methyl isoeugenol are respectively measured.
Respectively substituting the contents of isoeugenol methyl ether, 2,4, 5-trimethoxy-1-propenyl benzene, cyperenone, methyl eugenol and cis-methyl isoeugenol in rhizoma acori graminei into a formula:
PC1= -0.4900864 i-eugenol methyl ether +0.2739230 (2, 4, 5-trimethoxy-1-propenylbenzene) +0.2467422 cyperenone-0.5715808 methyl eugenol-0.5451560 cis-methyl isoeugenol;
PC2=0.26410931 isoeugenol methyl ether +0.69121906 (2, 4, 5-trimethoxy-1-propenylbenzene) -0.65153445 cyperenone-0.01786779 methyl eugenol-0.16627113 cis-methyl isoeugenol;
then judging the origin of the rhizoma acori graminei according to the numerical values of PC1 and PC 2;
when PC1= -2~1, PC2=0~1.5, the grassleaf sweelflag rhizome is produced in northern area; when PC1= -1.5~2, PC2= -2~3, the grassleaf sweelflag rhizome producing area is southern area; when PC1=1~2.5 and PC2= -1~0.5, the origin of Acorus gramineus soland is in the southwest region, and the results are shown in FIG. 7.
As can be seen from FIG. 7, the main components obtained from the experiment can distinguish the quality of Acorus tatarinowii Schott from different producing areas. Wherein, the quality of the southwest producing area is the best, the quality of the northern producing area is the second best, and the quality of the southern producing area is the worst.
8. Control of emulsification in rhizoma Acori Graminei extraction process
The compound of the 2 nd study "the partial components of the volatile oil were collected in large amounts 3 h before extraction" and the main components in the aromatic water were dissolved out in large amounts 4 h before extraction ", in combination with the 3 rd study" Benzene,1, 2-dimethoxy-4-propenyl-, (Z), 7- [2- (4-methoxy) ethyl ] -2-methyl-3-phenyl pyrazolo [1,5-a ] pyrimide is a uniquely distributed component in the volatile oil, which has a certain correlation with, but is not significant in, the distribution of the other components in the volatile oil; gamma-Asarone and caryophylelene are specific main components in aromatic water, and particularly, the extraction rule of gamma-Asarone has extremely high similarity with the distribution rule of the main components in aromatic water, so that the components are supposed to be specifically distributed in water, play the role of an emulsifier and further mediate a large amount of other components to be distributed in water, thereby increasing the emulsification phenomenon of the whole oil-water system and reducing the content of the main components in a volatile oil part. The method for controlling the emulsification phenomenon in the extraction process of the volatile oil of the grass-leaved sweetflag comprises the following steps:
weighing rhizoma Acori Graminei, adding 10 times of water, and extracting by steam distillation for 3-3.5 hr.
The extraction method can effectively control the content of the components in the aromatic water which plays the role of an emulsifier in the extraction process of the rhizoma acori graminei, thereby reducing the influence of the components on the volatile oil, improving the extraction rate and the quality of the volatile oil components, providing a reference for the high-efficiency extraction of the volatile oil of the traditional Chinese medicinal materials, and effectively improving the yield and the quality of the industrial large-scale production of the volatile oil.
It should be noted that when the following claims refer to numerical ranges, it should be understood that both endpoints of each numerical range and any numerical value between the two endpoints can be selected, and since the steps and methods adopted are the same as those in embodiments 1 to 3, the present invention describes preferred embodiments in order to prevent redundant description, but once a person skilled in the art knows the basic inventive concept, other changes and modifications can be made to these embodiments. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (8)
1. A method for evaluating the quality of acorus gramineus is characterized by comprising the following steps:
step 1, preparing a standard solution:
accurately weighing a tetradecanol standard substance, and adding absolute ethyl alcohol to a constant volume to obtain a tetradecanol standard substance solution; accurately weighing a docosane standard substance, and adding absolute ethyl alcohol to a constant volume to obtain a docosane standard substance solution;
step 2, preparing a test solution:
a. weighing rhizoma Acori Graminei, extracting by steam distillation, standing the extractive solution for layering, and separating the obtained oil phase and water phase;
b. adding absolute ethyl alcohol into the oil phase obtained by separation in the step a, diluting the obtained solution by 100 times by adding distilled water after the volume is constant to 10mL, and respectively adding the tetradecanol standard solution and the docosane standard solution in the step 1 to serve as volatile oil sample solutions;
c. taking the aqueous phase solution obtained by separation in the step a, and respectively adding the tetradecanol standard solution and the docosane standard solution prepared in the step 1 as aromatic water test sample solutions;
step 3, determination:
precisely absorbing the volatile oil test solution and the aromatic water test solution obtained in the step 2, and injecting the volatile oil test solution and the aromatic water test solution into a gas chromatography-mass spectrometer for determination, wherein the chromatographic conditions are as follows:
a chromatographic column: HP-5 MS quartz capillary column; temperature programming: initial temperature of 50 deg.C, holding for 2 min at 5 deg.C/min-1Increasing the speed to 110 ℃, keeping the speed for 2 min, and then increasing the speed to 2 ℃ for min-1The rate is increased to 120 ℃ and maintained for 5 min, then 4 ℃ min-1Raising the speed to 200 ℃, and keeping for 2 min; finally at 10 ℃ min-1The speed is increased to 280 ℃ and kept for 10 min;
mass spectrum conditions: selecting an EI ion source, wherein the scanning mass range is 30-500 amu, and the solvent delay time is 3 min;
step 4, analysis:
calculating and analyzing the relative content of the characteristic components in the volatile oil test solution and the aromatic water test solution and the total amount of the volatile oil by using a PCA method, and distinguishing the quality and/or the production area of the rhizoma acori graminei medicinal material according to the analysis result;
wherein the characteristic components are isoeugenol methyl ether, 2,4, 5-trimethoxy-1-propenyl benzene, cyperenone, methyl eugenol and cis-methyl isoeugenol.
2. The method for evaluating the quality of acorus gramineus soland according to claim 1, wherein the mass concentration of the tetradecanol standard solution in the step 1 is 2.06 mg-mL-1The mass concentration of the docosane standard solution is 2.06 mg-mL-1。
3. The method for evaluating the quality of acorus gramineus soland according to claim 1, wherein the extraction method of acorus gramineus soland in the step a is as follows: weighing rhizoma Acori Graminei, pulverizing, sieving with a first sieve, adding water 10 times of the total weight of rhizoma Acori Graminei, extracting for 6 hr by steam distillation, collecting extractive solution every 30 min, recording the volume of the collected solution, adding distilled water of equal volume into the extraction container, standing the extractive solution until oil and water are separated, and separating oil phase and water phase.
4. The method for evaluating the quality of acorus gramineus soland according to claim 1, wherein the volume ratio of the diluted constant volume solution to the tetradecanol standard solution and the docosane standard solution in step b is 100: 1.
5. The method for evaluating the quality of acorus gramineus soland according to claim 1, wherein the volume ratio of the aqueous phase solution to the tetradecanol standard solution and the docosane standard solution in step c is 1: 100.
6. The method for evaluating the quality of acorus gramineus soland according to claim 1, wherein in the step 3, the carrier gas is helium, the split ratio is 10:1, and the temperature of the injection port is 230 ℃; the ion source temperature is 230 ℃, the interface temperature is 250 ℃, and the quadrupole rod temperature is 150 ℃.
7. The method for evaluating the quality of acorus gramineus soland according to claim 1, wherein the relative content of volatile components is calculated by an internal standard method.
8. The method for controlling the extraction and emulsification of the volatile oil of rhizoma acori graminei according to the method for evaluating the quality of the rhizoma acori graminei as claimed in claim 1, wherein the specific control method comprises the following steps: weighing rhizoma Acori Graminei, adding 10 times of water, and extracting by steam distillation for 3-3.5 hr.
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